1 1 0 GR E E N C H E M I S TRY
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FROM WASTE TO WALL
Sustainable monomer improves performance of emulsion binders. By Simon Austin, Bob Foster and Martin Conrads,
Synthomer UK.
A new bio-based monomer, 2-octyl acrylate, has been derived
from a waste product of the processing of castor oil in alkyd
manufacture. It was substituted for n-butyl acrylate in three dif-
ferent types of emulsion. In all cases good polymerisation was
obtained and paints showed improvements in some properties.
M anufacturers are coming under increasing pressure from di-
rect customers, end consumers, competitors and regulatory
bodies to make their operations more compatible with sustainable
development, as defined in the Brundtland Commission report to the
United Nations in March 1987: ‘Sustainable development is development
that meets the needs of the present without compromising the ability of
future generations to meet their own needs’.
A 2010 study by the European Polymer Dispersion and Latex Associa-
tion (EPDLA) concluded that 80-90% of the environmental impact of
an emulsion polymerisation business can be directly attributed to the
raw materials consumed.
A polymer manufacturer can still improve business sustainability by
other means, such as reducing water usage, greenhouse gas emis-
sions, net waste and non-renewable energy consumption during
manufacture or transport. However, the most effective route towards
becoming truly sustainable is clearly to research, develop and pro-
E U R O P E AN CO AT I NGS J O UR N AL 03 – 2017
mote more sustainable monomers and other raw materials into the
market place.
KEY REQUIREMENTS FOR ‘GREENER’ MONOMERS
There are three primary criteria for new and more sustainable mono-
mers. Firstly, from a polymerisation viewpoint, the new monomers
must be easily processed and give clean, fully converted reactions. In
the end application the new monomers must offer performance com-
parable to current oil-based systems although, of course, enhanced
application properties would be still more advantageous.
Many of the developing monomers are relatively non-reactive and re-
quire special conditions – yet it is no use promoting a ‘sustainable’
monomer only to generate increased waste and use more energy in
the process.
Secondly, the new monomers must be readily available. Even if not
in large quantities initially, there must be a clear plan to upscale new
raw materials to meaningful quantities and within a defined timescale.
However, some novel monomers are still 5-20 years away from full
commercialisation.
Finally, the price must be relatively close – or projected to be relatively
close as volume increases – to that of current oil-based equivalents. Cur-
 G R EEN CHEM I S T RY 1 1 1

The monomer is inherently hydrophobic in nature compared to n-

RESULTS AT A GLANCE
űű A new bio-based monomer, 2-octyl acrylate, has been de-
rived from a waste product of the processing of castor oil. The
product is considered especially sustainable as the castor oil is
grown on land unsuitable for food crops.
űű Unlike some ‘sustainable’ monomers being developed, the
cost is only slightly above that of standard monomers.
űű It was evaluated by substituting it for n-butyl acrylate mon-
omer in three different types of emulsion: vinyl acetate/butyl
acrylate, styrene acrylic and pure acrylic copolymer.
űű In all cases good quality polymer was obtained without pro-
cessing difficulties. In basic tests of wall paint formulations of
differing gloss levels, no significant problems were found.
űű 2-octyl acrylate is highly hydrophobic, and this gave some
benefits in the form of reduced water uptake, better scrub re-
sistance and blanching resistance.
butyl acrylate (BA) for example, and would therefore be expected to
show some noticeable advantages in terms of water resistance prop-
erties over the oil-based BA monomer.
BASIS OF THE COMPARATIVE STUDY
Emulsion polymerisers typically have a wide range of polymers, cover-
ing many different monomer combinations, stabilising systems and
end target applications. In order to effectively screen new monomers,
careful consideration must be given to the selection of prototype pol-
ymer systems and the associated application testing.
The scale of the sample can also influence the end properties of the
polymer. Hence all samples described here were produced on the same
laboratory reactor. ‘Standard’ versions containing the oil-based acrylate
equivalent were also produced to give as fair a comparison as possible.
SATISFACTORY POLYMERISATION READILY OBTAINED
The first ‘standard’ reference system (S1) was a vinyl acetate/butyl
acrylate (VA/BA) copolymer at approximately 75/25 monomer ratio.
The polymer was conventionally stabilised with a protective colloid
(cellulose ether) and anionic/non-ionic surfactant package. With a
measured Tg of 16 °C and film forming temperature of 4 °C, the poly-
mer is intended for solvent-free interior paint systems. 

Figure 1: Production of 2-octyl acrylate from a sustainable source.

Castor oil CH 3-(CH 2) 7-OH

rently many ‘sustainable’ monomers under development are projected 2-octyl alcohol

to be two, four or even ten times the price of mainstream monomers.

Bio-based versions of the current acrylates (derived from crops, waste CH 3-(CH 2) 7-OH + CH 2=CH-COOH CH 3-(CH 2) 7-COO -CH=CH 2
wood or straw) are being introduced into the market place but even 2-octyl alcohol Acrylic acid 2-octyl acrylate

these have issues in terms of higher manufacturing costs, residual

impurities (which can inhibit polymerisation), and how to attribute the
perceived bio-content to a particular product or customer if absorbed
into bulk monomers.
It is likely that these bio-based monomers will, however continue to Figure 2: Vinyl acetate/acrylic emulsion water uptake over time.
increase in volume and so eventually reduce in cost towards that of
mainstream monomers.
Taking the view that increased exposure to the market can only be ben- 120
eficial in highlighting the work going on within the industry, Synthomer is
committed to evaluating and advancing any and all potential sustainable 100
monomers. Hence the focus of this paper is to detail an initial screening
of a new monomer, 2-octyl acrylate, in mainstream paints.
80
% Water uptake

NEW MONOMER IS DERIVED FROM WASTE BIO-PRODUCT

60
2-octyl acrylate (from Arkema) is produced by a patented process in-
volving the conversion of a chemical by-product from an already es- 40
tablished process. Figure 1 shows the basic process whereby 2-octyl
alcohol, as a waste product from castor-oil derived alkyd synthesis, is
20
reacted with acrylic acid to form 2-octyl acrylate, with an established
bio-content of 73%. Notably, the castor oil itself is only grown in areas
unsuitable for food crops. 0
0 4hr 24hr 48hr 7d
This method of manufacture is currently undergoing advanced scale
up trials. It is estimated that limited quantities will be available by the Standard VA 2
end of 2016 for larger scale polymerisation trials. The 2-OA monomer
VA 1 VA 3
currently has a cost estimated to be around 1.5 times that of oil-based
acrylates (such as n-butyl acrylate or 2-ethyl hexyl acrylate).

E U R OP E AN COAT I NGS JOU RN A L 03 – 2017

 1 1 2 GR E E N C H E M I S TRY

 In addition to the S1 system above, three variants with varying substi-
tution of BA by 2-octyl acrylate were also polymerised. The substitu-
tion was at 50% (VA1), 75% (VA2) and 100% (VA3) of BA, giving poly-
mers with a calculated bio-content of 8.5, 13.5 and 17.7% compared
to zero for the standard reference.
All four systems polymerised smoothly to give clean, low coagulum,
low free monomer systems. Table 1 details the emulsion and applica-
tion properties. Increasing substitution of BA by 2-OA (on a w/w basis)
leads to very slightly higher Tg and MFFT – this is due to the difference
in the theoretical values for BA (- 55 °C) and 2-OA (- 44 °C).
Particle size varies slightly, but is this is generally in line with expecta-
tions for a colloid-stabilised system. Overall the use of 2-OA leads to
lower emulsion viscosity in this system independently of particle size,
and this suggests the monomer may have an effect on other param-
eters such as the extent of colloid grafting.
Despite the hydrophobic nature of 2-OA no significant advantage in
water uptake (on the polymer films, Figure 2) was observed.
PAINT TEST RESULTS SUMMARISED
In the basic paint testing (Table 1) it can be seen that, although the
paint viscosity varied slightly, this could not be attributed either to par-
ticle size or to the emulsion viscosity. In contrast to the emulsion film
tests, there is a definite decrease in water uptake of the dried paint
films with increasing substitution of n-BA by 2-OA.
In the semi-gloss formulation a reduction in gloss could be seen with
increasing 2-OA levels; again, this is independent of particle size. How-
ever, gloss reduction can also arise from many interactions with other
raw materials in the paints and is being investigated further.
In the high PVC matt paint, properties such as viscosity, storage stabil-
ity, opacity etc. were similar to the standard. There is, however, a slight
but definite trend of improved scrub resistance with increasing 2-OA,
which would be expected from the more hydrophobic nature of the
monomer compared to n-BA.

Table 1: Vinyl acetate/acrylic – polymer and application properties. Table 2: Styrene/acrylic – polymer and application properties.

Raw material Standard ref. S1 VA 1 VA 2 VA 3 Raw material Standard SA 1 SA 2

Total solids content, % 56.8 57.7 57.4 56.9 ref. S2
Viscosity, mPas 4500 3140 2630 3315 Total solids content, % 50.0 50.0 49.4
Glass transition 16 16 16 17 Viscosity, mPas 77 161 245
temperature, ˚C
Glass transition temperature, ˚C 11 11 8
Minimum film formation 4 3 5 6
temperature, ˚C Minimum film 4 2 0
formation temperature, ˚C
Particle size µm 339 343 293 300
Particle size µm 148 131 130
Coagulum % 0.020 0.002 0.006 0.012
Semi-gloss paint S1 VA 1 VA2 VA3 Coagulum % 0.183 0.046 0.029
Viscosity, C+P (P) 0.9 0.9 0.8 0.9 High PVC matt
Viscosity, RTT (P) 13.9 13.0 14.5 14.0 Viscosity, C+P (P) 1.9 1.9 1.8
Gloss at 60˚ 73 73 68 58 Viscosity, mPas 17.4 17.8 17.4
Water uptake 30.9 28.6 21.4 21.1
Scrub resistance 24.8 26.8 19.1
High PVC matt EN ISO 11998 (µm) at 70% PVC
Scrub resistance 54.0 52.0 51.0 49.8 Scrub resistance 34.1 38.9 30.7
EN ISO 11998 (µm) EN ISO 11998 (µm) at 79% PVC

Figure 3: Styrene/acrylic water uptake over time. Figure 4: Pure acrylic water uptake over time.

40
60
% water uptake
% water uptake

40

20

20

0
0 4hr 24hr 48hr 7d
0
0 4hr 24hr 48hr 7d
Standard SA1 SA2
Standard PA 1 PA 2

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 G R EEN CHEM I S T RY 1 1 3

SATISFACTORY PERFORMANCE IN STYRENE ACRYLIC COPOLYMER The three systems polymerised smoothly to give clean, fully convert-
ed, low free monomer products. The particle size of the samples was
The second standard system (S2) is approximately 40/60 styrene/n- consistent (Table 3), as expected with an external seed polymerisation;
BA, conventionally stabilised with a standard anionic/non-ionic sur- however the 2-OA samples PA1 and PA2 both showed significantly in-
factant package. With a measured Tg of 11 °C and zero film-forming creased emulsion viscosity. Significantly lower water uptake was again
temperature the system is system is typical of a polymer intended for seen with 2-OA compared to n-BA (Figure 4).
high PVC solvent-free matt paints. PA1 (w/w substitution) gave a higher Tg/MFFT and lower elongation
Two versions of S2 were prepared. SA1 is a direct w/w substitution compared to the standard - this was expected due to the difference
of n-BA by 2-OA; SA2 is the same but with levels of 2-OA increased in theoretical Tg between the two monomers – however (as shown
to match the theoretical Tg of S2. These polymers had a calculated with PA2) this is easily rectified by the inclusion of slightly more 2-OA.
bio-content of 42% and 44% compared to zero for the standard, S1. Although the high shear viscosity of all three paints is similar there is
All three polymers polymerised smoothly with very good conversion, a definite increase in the low shear viscosity with the 2-OA paints (Ta-
and low end free monomer. Table 2 shows that the 2-OA samples (SA1 ble  3). This is to be expected, given that the more hydrophobic nature
and SA2) gave cleaner products, were finer in particle size and slightly of the monomer will show increased response to the HEUR thickener
higher in viscosity than the standard (S2). employed. Gloss in this system is consistent.
Despite the difference in theoretical Tg between the n-BA and 2-OA
samples the Tg of SA1 (w/w substitution) was similar to the standard GOOD PERFORMANCE OBTAINED,
and with slightly lower film forming temperature. SA2 (higher 2-OA) REASONABLE COST PREDICTED
showed a further reduction in both Tg and MFFT.
A significant advantage in lower water uptake (Figure 3) was observed As discussed above, there are three main areas for consideration
with SA1 and SA2 over the standard. Although the basic emulsion sta- when introducing new, more sustainable, raw materials into main-
bility of all three samples was similar, the 2-OA versions gave notice- stream emulsion polymerisation. In all three aspects the new mono-
ably better stability to silicone emulsions than the n-BA standard. mer achieves good results.
Here the basic paint properties (Table 2) were similar with all three 2-octyl acrylate was directly substituted into a number of polymer for-
emulsions showing identical viscosity and good storage stability. Var- mulations and shows proven compatibility with a variety of monomers
ied scrub resistance results were obtained; however it would still be and stabilising systems. The resultant products polymerised smoothly
expected that, overall, a slight advantage should be seen with 2-OA and gave clean, fully converted polymers.
compared to n-BA. Application results showed that there were no significant drawbacks
in using 2-octyl acrylate and, indeed, in many systems the more hydro-
MONOMER IS ALSO EFFECTIVE IN PURE ACRYLIC COPOLYMER phobic nature of the monomer could be of benefit in terms of better
blanching resistance, lower water uptake, higher response to HEUR
This standard system (S3) was a 50/50 MMA/n-BA system, convention- thickeners and possibly scrub resistance.
ally stabilised with an anionic/non-ionic surfactant package/functional The commercial process involved in manufacturing 2-octyl acrylate by
monomers, and produced via an external seed method. a sustainable route is patented and is currently undergoing upscaling.
As with the styrene acrylate above, two versions of the standard rec- The monomer is expected to become more widely available from the
ipe were produced on 2-OA: the first (PA1) was a direct w/w substi- end of 2016.
tution of n-BA, the second (PA2) was full substitution but with 2-OA The indicative price of the monomer is currently higher than oil-based
increased to match the theoretical Tg of the reference standard, S3. acrylates (by a factor of about 1.5) but this is expected to come down
Initial tests on these systems were carried out in a low (20%) PVC paint as the availability increases. In addition it is expected that the hydro-
formulation. phobic nature of the monomer will particularly lend itself to more spe-
cialist applications such as furniture coatings, where a higher initial
cost might reasonably be borne.
More in-depth work is being carried out in this area and may be sub-
ject to further publication. In addition, the company has an ongoing
Table 3: Pure acrylic – polymer and application properties programme of work to identify and bring forward novel monomers to
ensure that the sustainability of emulsion polymerisation increases
Raw material Standard towards the future.  
PA 1 PA2
ref. S3
Total solids content, % 49.9 50.8 50.1
Viscosity, mPas 2180 6340 6560
Glass transition temperature, ˚C 23 28 22
Minimum film formation
19 27 21
temperature, ˚C
Particle size µm 99 98 98
Coagulum % 0.15 0.05 0.2 BOOK TIP
20% PVC gloss
Acrylic Resins
Viscosity, C+P (P) % 0.4 0.4 0.4
U. POTH / R. SCHWALM / M. SCHWARTZ
Viscosity, RTT (P) 12.4 14.6 14.1
383 PAGES
Gloss at 60˚ 76 76 78 ISBN: 9783866308572
Elongation, F-max (%) 235 200 230 ORDER NO.: 518
Water uptake 7.9 6.0 6.8

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1 1 4 GR E E N C H E M I S TRY

“Replacement of oil-based
acrylates by 2-OA on a
1:1 basis had little impact on
application due to temperature.“

Simon Austin
Technical Ser vice Manager Coatings, SBU
3 questions to Simon Austin Functional Solutions
Synthomer
Styrene acrylic copolymers are widely used in architectural applications. How does the simon.austin@synthomer.com
higher content of 2-OA impact the processing regarding the temperature range in archi-
tectural applications? Replacement of oil-based acrylates by 2-OA on a 1:1 basis had only minor
effect on Tg/MFFT and therefore little impact on application due to temperature. Futhermore it was
simple to adjust 2-OA level to give comparable Tg/MFFT values to the original oil-based polymers if
necessary.

What is your definition of a low paint formulation, and why was it used for testing the
pure acrylic copolymer alternative? The low PVC formulation was chosen for the pure acrylic
evaluations because this was a simple recipe with the highest binder content, and so should highlight
differences in elongation and water pick up. It also gave the opportunity to assess HEUR thickener
response of the different monomers.

The difference in shear viscosity demands an adequate solution in the rheological as-
pects of the formulation. How you would describe the chemistry of a suitable thickener?
In mainstream wallpaints, containing HASE and HEC thickeners, little difference was seen between
the polymer types in terms of end formulation viscosity. Some consideration is, however, required,
when using HEUR thickeners as these are prone to viscosity variation due to changes in monomer/
polymer type.

E U R O P E AN CO AT I NGS J O UR N AL 03 – 2017